Chlorotrimethylsilane → HCID 12769232, compound

HRID 978906Notes

Reaction equation

HRID 978906 reaction equation
C([Li])CCC.C(NC(C)C)(C)C.[CH3:13][C:14]1([CH3:23])[O:21][CH2:20][CH2:19][CH:18]2[N:15]1[C:16](=[O:22])[CH2:17]2.[N-:24]=[N+:25]=[N-:26].C[Si](Cl)(C)C>CCCCCC.O1CCCC1>[CH3:13][C:14]1([CH3:23])[O:21][CH2:20][CH2:19][CH:18]2[N:15]1[C:16](=[O:22])[CH:17]2[N:24]=[N+:25]=[N-:26]

Participants

8

Reactant 5

HCID 6397ChlorotrimethylsilaneHCID 7912DiisopropylamineHCID 33558AzideHCID 12769229HCID 12769229, compoundHCID 178418339Butyllithium

Product 1

HCID 12769232HCID 12769232, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Procedure

In a nitrogen stream under stirring, 50 ml of dry tetrahydrofuran is cooled to -78° C. and, then, 20 ml of a solution of 15% n-butyllithium in n-hexane is added thereto. After dropwise addition of 3.66 ml of diisopropylamine, the mixture is stirred at -78° C. for 15 minutes. A solution of 3.1 g of 2,2-dimethyl-1-aza-3-oxabicyclo[4.2.0]octan-8-one in 15 ml of dry tetrahydrofuran is added dropwise and the mixture is stirred at -78° C. for one hour. Then, a solution of 4.34 g of p-toluenesolfonyl azide in 15 ml of dry tetrahydrofuran is added dropwise and the mixture is stirred at -50° C. to -60° C. for 1.5 hours. To this mixture 5.1 ml of trimethylsilyl chloride is added dropwise and the reaction mixture is heated under reflux for 5 hours. Ater cooling, the insolubles are filtered off and the filtrate is concentrated under reduced pressure. The residue is shaken with water and ethyl acetate and the ethyl acetate layer is separated, washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The solvent is then distilled off and the residue is purified by silica gel column chromatography to give 2,2-dimethyl-7-azido-1-aza-3-oxabicyclo[4.2.0]-octan-8-one as a 1:4 mixture of cis- and trans-isomers.

Workup

  1. stirringthe mixture is stirred at -78° C. for 15 minutes
  2. stirringthe mixture is stirred at -78° C. for one hour
  3. stirringthe mixture is stirred at -50° C. to -60° C. for 1.5 hours
  4. temperaturethe reaction mixture is heated
  5. temperatureunder reflux for 5 hours
  6. temperatureAter cooling
  7. filtrationthe insolubles are filtered off
  8. concentrationthe filtrate is concentrated under reduced pressure
  9. stirringThe residue is shaken with water and ethyl acetate
  10. customthe ethyl acetate layer is separated
  11. washwashed with water
  12. dry with materialdried over anhydrous sodium sulfate
  13. concentrationconcentrated under reduced pressure
  14. distillationThe solvent is then distilled off
  15. customthe residue is purified by silica gel column chromatography

Sources & evidence

ORD record
ord-d6a72ac4ca46423aa7a18249886a3a90
Source dataset
uspto-grants-1987_05
Patent number
US04665067

Reaction notes

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